KR100470952B1 - Polymerisation method - Google Patents

Abstract

A method for making a polymer or oligomer comprising the steps of making a first monomer comprising a substituted aromatic or heteroaromatic group by providing an aromatic or heteroaromatic group substituted with first and second director groups, performing metalisation at a first position on the aromatic or heteroaromatic group, performing electrophilic substitution so as to provide a first substituent group at the first position, and contacting in a reaction mixture the first monomer with at least two further monomers that independently are the same or different from the first monomer under conditions so as to form a polymer or oligomer, wherein the nature and positions of the first and second director groups regioselect the first position.

Description

Polymerization method {POLYMERISATION METHOD}

The present invention relates to a process for producing a polymer or oligomer and to a polymer or oligomer that can be produced by the process. Uses of such polymers or oligomers are also provided.

More specifically, the present invention is directed to conjugated molecules, oligomers and polymers for electrical, electronic, optical and optoelectronic devices, for example small molecules such as light emitting diodes (LEDs) and polymer based light emitting devices. It is about. In particular, the present invention relates to methods of synthesizing aromatic precursors that produce luminescent conjugated molecules, oligomers, macromolecules and polymers when bound in a controlled C-C bond generation process.

High luminous efficiency in the solid state is an essential condition for (electroluminescent) organic semiconductors that can emit light by injection of charge under an applied field. Methods of providing aromatic precursor molecules suitable for participating in polymerization coupling reactions are advantageous for designing novel conjugated systems for applications in light emitting devices. At present, a great deal of evidence has been found to improve photoluminescence efficiency by diversifying the substitution scheme.

Various known methods exist for coupling aromatic monomers to obtain conjugated polymers or oligomers, in particular for use in light emitting devices. One such method is the Gilch dehydrohalogenation polycondensation of 1,4-bis (halomethyl) aromatic derivatives. This is the way Papers ( J. Poly Sci . 1-A, 1966, 4, 1337), US Patent No. 5,189,136 (1990) to Woodl, H. Spreitzer, W. Kreuder, H. Becker and H. Schoo), International Publication No. 98/27136, by Becker et al. (H. Becker, H. Spreitzer, K. Ibrom and W. Kreuder) ( Macromolecules , 1999, 32, 4925-4932). Is disclosed. The long-term dehydrohalogenation method is particularly dependent on either of the radical bromination of the corresponding dimethyl derivative or the halomethylation of the reactive precursor. In the former case, the yield should be reduced due to the electrophilic halogenation of the aromatic ring. This problem especially arises when additional substituents are present on the aromatic ring that can activate the electrophilic substitution reaction. In the latter case, an electron-rich aromatic precursor is required to increase the yield of the halomethylation reaction. Halomethylation reactions are particularly unsuitable for mass production because methyl halomethyl ether (where the halogen is chlorine or bromine), a potential carcinogen, is likely to be produced during the manufacturing process.

Other known polymerization reactions include boronic acid derivatives as described in Schluter and Wegner's paper ( Acta Polym ., 1993, 44, 59) and (Pd catalysts of vinyl halides and aryl halides). There is a Suzuki crosslink). This reaction is often referred to as "Suzuki" polymerization.

Another known polymerization reaction is Morner Wittig polycondensation of bis (phosphonates) and dicarbonyl compounds. This method is described in International Application Publication Nos. 96/10617 (1996) and Chem. Abstr. , 1996, 124, 345038u.

Yamamoto's paper ( Progr. Polym. Sci ., 1992, 17, 1153) discloses another polymerization reaction involving the crosslinking of aromatic dibromo derivatives using nickel catalysts. This reaction is often called "Yamato" polymerization.

Polymerization by the McMurry coupling reaction of dicarbonyl derivatives was carried out in Abstracts of Papers of the American Chemical Society, 1998, Vol. 215 (Pt2), pp.322-POLY and Daik et al . ( New J Chem ., 1998, 22, 1047).

Synthesis of certain monomers for use in the aforementioned polymerization reactions will be appreciated by those skilled in the art. This results in limiting the range of polymers obtainable by these polymerization reactions.

Poly (p-arylene vinylene) (PPV) is generally disclosed in WO 98/27136.

Synthetic Metals, 101, (1999) 216-217 discloses silyl disubstituted PPV derivatives. The two silyl substituents are identical to each other. Poly [2,5-bis (dimethyloctyl silyl) -1,4-phenylene- via dehydrohalogenation condensation polymerization from 2,5-bis (bromomethyl) -1,4-bis (dimethyloctyl silyl) benzene Vinylene] polymer.

Outside the field of polymerization, for example, Snieckus's paper (Pure Appl. Chem., 1994, 66, 2155), Paper et al . ( J. Org. Chem ., 1998, 63, 1514) And in a paper by Snickus ( Chem. Rev. , 1990, 90, 879-933) report a concept on the direct metallization of bis-carbamate and urethane. However, this concept has not been disclosed or suggested as one step in the process of making polymers or oligomers.

The inventors have identified the need to provide an improved process for providing monomers for use in the aforementioned polymerization reactions.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

FIG. 1 shows absorption, electroluminescence (EL) and photoluminescence (PL) spectra of a C ₈ C ₁₀ polymer, where au represents an arbitrary unit.

2 shows absorption spectra of C ₈ C ₁₀ , C ₈ C ₈ , C ₁₀ C ₁₀ and DMOS-PPV polymers, respectively.

3 shows electroluminescence (EL) spectra of C ₈ C ₁₀ , C ₈ C ₈ , C ₁₀ C ₁₀ and DMOS-PPV polymers, respectively.

4 shows photoluminescence (PL) spectra of C ₈ C ₁₀ , C ₈ C ₈ , C ₁₀ C ₁₀ and DMOS-PPV polymers, respectively.

5 shows the current density and luminescence of a device composed of C ₈ C ₁₀ polymer, PEDOT: PSS layer and Al cathode.

FIG. 6 shows an electroluminescence spectrum of Polymer 12 measured in an LED structure including a PEDOT: PSS hole injection layer and an Al cathode.

It is therefore an object of the present invention to provide an improved method for producing a polymer or oligomer.

It is a further object of the present invention to provide polymers and oligomers which can be prepared and produced by the improved process.

It is another object of the present invention to provide an optical device or component thereof comprising the polymer and oligomer of the present invention.

Another object of the present invention is to provide the use of a polymer which is the subject of the present invention.

Finally, another object of the present invention is to provide a method of fabricating an optical device or a component thereof using the polymer of the present invention.

Thus, in a first aspect of the invention i) preparing an aromatic group or heteroaromatic group substituted with first and second director groups, ii) at a first position of the aromatic group or heteroaromatic group Performing a metallization reaction and iii) conducting an electrophilic substitution reaction to introduce the first substituent at the first position to produce a first monomer comprising a substituted or heteroaromatic group; (a) and contacting said first monomer with at least two additional monomers, each of which is the same as or different from said first monomer, under conditions for producing a polymer or oligo monomer in said reaction mixture; The method of producing a polymer or oligomer is provided wherein the properties and locations of the first and second director groups are regioselected to the first location.

In a second aspect of the invention there is provided a polymer or oligomer, preferably soluble, prepared according to the method defined in the first aspect.

In a third aspect of the invention, it can be prepared according to the method defined in the first aspect, and includes an aromatic group or heteroaromatic group having first and second bonding positions and first and second director groups X and Y. There is provided a polymer or oligomer which is preferably soluble, having repeating units. Wherein X is ortho to the first bond position, Y is ortho to the second bond position, X and Y are the same or different from each other, and each represents a hydroxy group, an alkoxy group, an alkoxyalkyl group, an amide group, or a halide group. , Haloalkyl group, amine group, aminoalkyl group, carboxylic ester group, urethane group, carbamic acid group, sulfonamide group, sulfurylalkyl group or carbamide group, A is C, O, S or NR and n = 0, or Or A is C or NR, B is C or NR, n = 1 and R is a hydrocarbyl having a pendant group, preferably optionally at least one hetero atom.

In a fourth aspect of the invention the process defined in the first aspect having a repeating unit comprising a substituted or unsubstituted vinylene group and an aromatic group having a first and second silyl substituents X 'and Y' or a heteroaromatic group A soluble polymer or oligomer, which can be prepared according to the present invention, is provided, wherein X 'and Y' are different from each other, X 'is ortho with respect to the first binding position, and Y' is ortho with respect to the vinylene group. to be.

In a fifth aspect of the invention, the positive charge carrier and the negative charge carrier are positioned between the first charge carrier injection layer (anode) for injection of a positive charge carrier, the second charge carrier injection layer (anode) for injection of a negative charge carrier, and these charge injection layers. It includes a light emitting layer that receives and combines to emit light, wherein the light emitting layer comprises a polymer or oligomer as defined in any one of the second, third and fourth aspect of the present invention An optical device or a component thereof is provided.

In a sixth aspect of the invention there is provided the use of a polymer or oligomer for optical devices as defined in any of the aspects of the second, third and fourth aspects of the invention.

In a seventh aspect of the invention, a process (a) for providing a polymer or oligomer as defined in the second, third and fourth aspects of the invention and including the polymer or oligomer as an optical device or component thereof The manufacturing method of the optical apparatus or its component containing the process (b) to make is provided.

In the first aspect, the present invention provides an efficient method for synthesizing a monomer comprising a substituted or heteroaromatic group for producing a polymer or oligomer by polymerization. One of the advantages of the method is the ability to introduce substituents sequentially and thus control the substituents which may be different from one another.

For the purposes of the present invention, the term "oligomer" includes high order oligomers up to trimers, tetramers, and maximum pentomers. The term "polymer" includes all materials having a greater degree of polymerization than oligomers.

In addition, for the purposes of the present invention, the term "aromatic group or heteroaromatic group" includes mononuclear aromatic groups and multinuclear aromatic groups. The mononuclear aromatic group has one aromatic ring, for example, phenyl or phenylene. Multinuclear aromatic groups are those having two or more aromatic groups, each fused with one another (e.g., naphthalene, quinoline or indole), each covalently bonded (e.g., biphenyl) and / or one fused with one aromatic covalently. It can be a combination of rings. It is preferred that the aromatic group or heteroaromatic group is substantially all groups substantially conjugated.

Metallization of the first position in step (ii) may be carried out by substituting a suitable group, for example hydrogen or halogen (eg Cl, I or Br). However, it is preferable to metallize by substituting hydrogen in the first position.

The first substituent is introduced at the first position in step (iii). The first substituent may be introduced directly to the first position via an electrophilic substitution reaction. Alternatively, the first substituent may be introduced via an electrophilic substitution reaction followed by one or more additional steps.

This method is particularly suitable for functionalizing aromatic groups or heteroaromatic groups in a manner that cannot be readily realized by alternative synthesis strategies. In this respect, there has been a difficulty in preparing asymmetrically substituted aromatic groups or heteroaromatic groups. Asymmetric ring substitution of aromatic or heteroaromatic groups, in particular polyarylene vinylene, is expected to disrupt the packing between the chains. If such groups are included asymmetrically in polymers or oligomers, this is luminous efficiency as discussed in the paper by Anderson et al. (MR Andersson G. Yu and AJ Heeger) ( Synth. Met ., 1997, 85, 1275). To improve.

Polymer DMOS-PPV 6, as known by H. et al. (D.-H. Hwang, ST Kim, HK Shim, AB Holmes, SCMoratti and RH Friend), Chem. Commun ., 1996, 2241-2242 It can be prepared in high yield according to the method. This can be seen from the scheme shown below.

In a second embodiment of the first aspect of the invention, process (a) is carried out by carrying out an electrophilic substitution reaction and (iv) performing metallization at the second position of the aromatic group or heteroaromatic group. (V) further comprising introducing a second substituent at the 2 position. Herein, the characteristics and positions of the first and second directors select a second position.

Metallization of the second position in step (iv) can be carried out by substituting a suitable group, for example hydrogen or halogen (eg Cl, I or Br). However, it is preferable to metallize by substituting hydrogen in the second position.

The second substituent is introduced at the second position in step (v). The second substituent may be introduced directly to the second position via an electrophilic substitution reaction. Alternatively, the second substituent may be introduced via an electrophilic substitution reaction followed by one or more additional steps.

The first and second substituents are the same or different from each other. Preferably, the first and second substituents are different from each other.

In the process of the invention the first and / or second substituents are halides, B (OH) ₂ , B (OR) ₂ , alkoxy, alkoxyalkyl, alkyl, hydroxy, aryl, heteroaryl, SnR ₃ , silyl, amide And COCF ₃ . Among these groups, the first and / or second substituents are more preferably selected from the group consisting of Br, I, SiMe ₂ C ₈ H ₁₇ , SiMe ₂ C ₁₀ H ₂₁ and SiMe ₃ , respectively.

It is preferable that the said aromatic group or heteroaromatic group is substituted asymmetrically.

In the metallization step of the process of the present invention, metallization is a suitable organometallic derivative such as organolithium derivative or tin, boronic acid or ester, copper reagent (Cu ⁺¹ ), zinc reagent (Zn ⁺² ), magnesium reagent (Mg ⁺² ) or nickel reagent (Ni ⁺² , Ni ⁰ ) can be added to the reaction mixture. However, organolithium is preferred, and t-BuLi is most preferred.

In the case of metallization by substituting hydrogen, it is preferable to add an organolithium derivative to the reaction mixture and then metallize by trans metalation using a reagent as described above as necessary.

In the method of the present invention, the steric and inductive effects of the characteristics and positions of the first and second director groups should be considered.

Preferably, the characteristics and positions of the first and second director groups are selected so that the first position becomes ortho with respect to the first director group.

In addition, it is preferable that the characteristics and positions of the first and the first director groups are selected so that the second position becomes ortho with respect to the second director group.

Possible schemes when the characteristics and positions of the first and second director groups are selected to be ortho to the first director group and the second position to be ortho to the second director group are as follows.

E is for example Br, I, B (OH) ₂ , B (OR) ₂ , OR, OH, Ar, R, heteroaromatic group, SnR ₃ , SiR ₃ , SiR ₁ R ₂ R ₃ , NR ₂ or COCF ₃ and R is a hydrocarbyl having a pendant group, preferably at least one hetero atom, if necessary.

Similar reactions can be considered for any heteroaromatic or aromatic starting material suitably functionalized with two “director groups”. Specifically, routes involving substituted fluorene derivatives and naphthalene derivatives may be convenient.

The first and second director groups are the same or different from each other.

The first and second director groups are each an alkoxy group, an alkoxyalkyl group, an amide group, a halide group, a haloalkyl group, an amino group, an aminoalkyl, a carboxylic ester group, a urethane, a carbamic acid group, a sulfonamide, a sulfurylalkyl group, or a carbamide. It is advantageously selected from the group consisting of groups.

In the method of the present invention, the first and second director groups are preferably selected from the group consisting of CONEt ₂ , CONHCMe ₂ Ph, OCONMeCMe ₂ Ph, OCONEt ₂ and SO ₂ NHCMe ₂ Ph SO ₂ -t-Bu, respectively. Do.

N, N -diethylcarboxamide (-CONEt ₂ ) and urethane (eg -OCONEt ₂ ) director groups are directly metallized to adjacent (ortho) positions, for example using t-butyllithium. Can be used for The resulting organolithium can be alkylated, silylated, boronated or tinned and converted to organometallic derivatives to create new CC bonds in the aromatic ring. The resulting metal derivative can be crosslinked with a suitable precursor during the polymerization reaction.

In a third embodiment according to the first aspect of the invention, process (a) polymerizes by converting one or both of the director groups and / or one or both of the first and second substituents to a reactive group And (vi) producing a monomer having two reactive groups capable of participating in.

When one or both of the director groups and / or one or both of the first and second substituents are converted to a reactive group capable of participating in one of the aforementioned crosslinking polymerization reactions, the method of the invention Provided are a variety of novel substituted monomers that can be used in the synthesis of conjugated luminescent oligomers and polymers.

The conversion reaction in step (vi) can be through one or several chemical conversion steps.

Suitably the two reactive groups are in para position with one another.

Carboxamide director groups can be reduced to tertiary amines and finally converted to CH ₂ Cl or CH ₂ Br for lengthwise polymerization. Degradation of urethane director groups to phenols, conversion to triflate, and metal-mediated crosslinking reactions resulted in poly (arylene), poly (arylene-vinylene) by Heck reaction, or (e.g.) or Sonogashira polycondensation produces poly (arylene-ethylene).

Many aromatic and heteroaromatic precursors can be prepared in accordance with the present invention. The boronate and halo substituted precursors for Suzuki crosslinking of substituted fluorene derivatives can be prepared by methods of inducing novel conjugated materials. Tin precursors are suitable for use in Stille crosslinked polymerization. Preferably, the process of the invention can be used for the preparation of bis (halomethyl) precursors for prolonged dehydrohalogenation.

According to the method of the present invention, the reaction of the metalized derivative with CF ₃ CO ₂ Et produces a corresponding mono- or bis-trifluoroacetyl substituted derivative and the new CF ₃ by Horner condensation polymerization. To produce substituted poly (arylene vinylene) derivatives.

In certain examples of the third embodiment, each director group may be converted to a phosphonate, carbonyl, triflate or halomethyl reactive group, respectively. When each director group is each converted to a halomethyl group, the first monomer is suitable for use in the above-mentioned long-length dehydrohalogenation reaction.

Classes of polymers or oligomers that may be suitably prepared according to the second aspect of the invention include polymers or oligomers comprising arylene vinylene repeat units derived from a first monomer. It is preferable that the said arylene vinylene repeating unit contains a phenylene vinylene group.

In another specific example of this embodiment, each substituent is independently converted to a halide reactive group. Thus, the first monomer can advantageously participate in the aforementioned "Yamamoto" polymerization or "Suzuki" polymerization.

Another class of polymers or oligomers that can be conveniently prepared according to the second aspect of the invention by the process is a polymer or oligomer comprising phenylene repeat units derived from the first monomer.

A polymer or oligomer prepared according to the process described in the first aspect of the invention is provided in a second aspect of the invention.

In a third aspect of the invention, the two bonding positions are preferably para to each other. The bonding position is a position on an aromatic group or heteroaromatic group which is covalently bonded (usually a CC bond) to an additional group in the polymer or oligomer chain. to be.

It is preferable that the said aromatic group or heteroaromatic group further contains the group of the following general formula (I).

The polymer or oligomer according to the third aspect of the present invention has a repeating unit comprising an aromatic group or a heteroaromatic group comprising a group of the following general formula II.

In a third aspect of the invention, the first and second director groups X and Y may be as defined above with respect to the first aspect of the invention.

The oligomers or polymers according to the third aspect of the invention are polymers or oligomers which are emissive, preferably luminescent and more preferably have a band gap in the range of 1.5 eV to 3.5 eV.

In accordance with a third aspect of the present invention, polymers and oligomers of particular interest are those shown below.

or

Wherein A and B are the same or different and are each H or alkyl, cyclic or branched alkyl, n is in the range of 2 to 100, preferably n is about 6, 1 <a <10, preferably A is 1, 1 <b <10, preferably b is 1.

The C9 substituents A and B of the fluorene comonomer may be selected to improve the solubility of the polymer or oligomer. Preferred C9 substituents in this respect are C ₆ H ₁₃ and C ₈ H ₁₇ .

In the fourth aspect of the present invention, the polymer or oligomer preferably has a repeating unit containing a group represented by the following general formula (III).

X 'is SiR ₁ R ₂ R ₃ , Y' is SiR ' ₁ R' ₂ R ' ₃ , and R ₁ , R ₂ , R ₃ , R' ₁ , R ' ₂ and R' ₃ are each alkyl. Or cycloalkyl. It is more preferable that X 'and Y' are each independently SiMe ₂ C ₁₀ H ₂₁ or SiMe ₂ C ₈ H ₁₇ .

In accordance with a fourth aspect of the invention, the polymer of particular interest comprises a homopolymer. The term "homopolymer" means that it is made from one type of monomer. In this regard, monomers are distinguished from repeat units because homopolymers can be defined as having one or more different repeat units.

 The homopolymer is preferably the following structural formula.

or

In the formula, n is 4 to 200, preferably 4 to 100.

The polymer or oligomer according to the fourth aspect of the present invention is preferably a light emitting polymer or oligomer. More preferably, the polymer or oligomer has a band gap in the range of 1.5 eV to 3.5 eV.

A fifth aspect of the present invention is to provide an optical device or component thereof comprising a substrate and a polymer according to the second, third and fourth aspects of the invention carried on the substrate.

In the fifth aspect, the provided optical device or component thereof is positioned between an anode, a cathode, and if necessary, one or more charge transport layers and between the anode and the cathode to receive and bind the positive charge carriers and the negative charge carriers. It includes a light emitting layer for generating a light emitting layer, wherein the light emitting layer comprises a polymer or oligomer according to any one of the second, third and fourth aspect of the present invention.

Preferably the cathode material has a work function suitable for injecting electrons, for example Ca, Al, LiF-Al or CsF-Al. In addition, the positive electrode material preferably has a work function suitable for injecting protons.

The optical device or component thereof preferably comprises an electroluminescent device.

In the sixth aspect of the present invention, when the polymer or oligomer according to any one of the second, third and fourth aspects of the present invention is used in an optical device, the optical device includes an electroluminescent device. desirable.

The invention also provides the use of a polymer or oligomer as a light emitting material as defined in connection with the second, third and fourth aspects.

The reaction scheme shown below illustrates the conversion step (vi).

The above scheme illustrates the metallization of bis-amide 1 to obtain bis-metalized derivatives and finally to the bis-silyl precursor 2. This precursor is then polymerized to produce the corresponding conjugated polymer. The above example obtains a poly (2,5-bisdimethyloctylsilyl-1,4-phenylenevinylene) derivative. An advantage of the process of the present invention is the synthesis of high yield precursor 3, which avoids the carcinogenic chloromethyl methyl ether.

In principle, any of the homologues of precursor 2 with aryl or heteroaryl groups can be prepared via C-C coupling reactions.

FIG. 6, which will be described later, illustrates an electroluminescence spectrum of polymer 12 measured in an LED structure including a PEDOT: PSS hole injection layer and an aluminum cathode.

The following precursor 7 comprising an asymmetric phenylene group is prepared with surprising efficiency. Precursor 7 is converted to a "C ₈ C ₁₀ polymer" which is a highly luminescent asymmetric substituted PPV derivative. Poly (2,5-bisdimethyldecylsilyl-1,4-phenylene vinylene) ("C ₁₀ C ₁₀ polymer") is also prepared.

The above examples include poly (2-dimethyloctylsilyl-1,4-phenylene-vinylene) CDMOS-PPV (polymer 6) and poly (2,5-bisdimethyloctyl) as well as the synthesis of asymmetric C ₈ H ₁₀ polymer 8 The synthesis of silyl-1,4-phenylene) -vinylene (C ₈ C ₈ polymer 4) and C ₁₀ C ₁₀ polymer 13 is also illustrative. These polymers exhibit PL efficiencies in the solid state in the range of 47-57% and can be fabricated as emitting layers of polymer LEDs whose metal contacts are ITO and Al (on glass).

The absorption spectra of C ₈ C ₁₀ polymer 8, C ₁₀ C ₁₀ polymer 13 and DMOS-PPV 6 are very similar (both in peak wavelength and relative intensity of properties). However, C ₈ C ₈ Polymer 3 not only exhibits a blue-shift of 8 mm or more compared to other spectra, but also more pronounced UV properties.

Both EL and PL spectra are very similar for all four polymers, with the longest wavelength of the first peak for DMOS-PPV 6 and the shortest for C ₈ C ₁₀ polymer 8. In these two spectra, the electromagnetic vibration structure is well separated and there is no sign of interference effects in the microcavities that change the spectrum. PL efficiency is reported.

The scheme shown below further illustrates the conversion step (vi).

Suzuki crosslinking between monomer 10 and related carbamates produces blue light emitting materials 11 and 12, respectively. Evidence of emission in the UV region of the spectrum is detected.

Example 1

2-dimethyloctylsilyl-tetra- N Preparation of -ethyl-terephthalamide

t-butyllithium (253 ml, 0.43 mmol) was added to tetra- N -ethyl-terephthalamide (100 mg, 0.36 mmol) dissolved in 30 ml of anhydrous tetrahydrofuran and cooled with acetone-nitrogen bath. After 30 minutes, chlorodimethyloctylsilane (102 ml, 0.43 mmol) was added. The reaction mixture was left for 3 hours until the temperature of the bath reached room temperature. A saturated aqueous sodium chloride solution was added and extracted with dichloromethane. The organic layer was dried over magnesium sulfate and concentrated in vacuo. Column chromatography was performed using hexane / ethyl acetate (60/40) as eluent [Rf = 0.54, hexane / ethyl acetate (85/25)] to give a white solid (yield 78%). mp = 46 ° C.

Spectral results

IR (KBr) (cm ^-1 ): 2972, 2926, 2854, 1623, 1484, 1430, 1383, 1291, 1251, 1220, 1105, 1062, 842

¹ H-NMR δ _H (CDCl ₃ , 250 MHz) 7.40 (d, 1H, J = 1.57 Hz), 7.22 (dd, 1H, J ₁ = 7.75 Hz, J ₂ = 1.57 Hz), 7.09 (d, 1H, J = 7.75 Hz), 3.45-3.36 (m, 4H), 3.06-2.98 (m, 4H), 1.15-0.90 (m, 25H), 0.74-0.64 (m, 4H), 0.12 (s, 6H)

¹³ C-NMR δ _C (CDCl ₃ , 62.5 MHz) 171.6, 171.0, 143.6, 137.4, 136.5, 132.8, 126.3, 125.6, 43.4, 38.9, 33.5, 31.8, 29.2, 29.1, 23.8, 22.5, 15.9, 14.0, 13.6 , 12.7, -2.3

Mass spectrometry: (CI) m / z 447.3400 ( M ⁺ ) C ₄₀ H ₈₀ N ₂ O ₂ Si required M 446.7400

Measured value C: 69.99%, H: 10.22%, N: 6.27%

Calculated Value C: 69.90%, H: 10.39%, N: 6.27%

Example 2

2-dimethyloctylsilyl-5-dimethyldecylsilyl-tetra- N Preparation of -ethyl-terephthalamide

At −78 ° C. sec -butyllithium (2.9 ml, 3.7 mmol) was added to a solution in which tetramethylethylenediamine (0.55 ml, 3.7 mmol) was dissolved in 15 ml of anhydrous tetrahydrofuran, 15 ml of anhydrous tetrahydrofuran 2-dimethyloctylyl-tetra- N -ethyl terephthalamide (1.26 g, 2.8 mmol) dissolved in was added dropwise and the reaction mixture was stirred at -78 ° C for 20 minutes. Chlorodimethyloctylsilane (1 ml, 3.7 mmol) was added and allowed to stand overnight at room temperature in a bath. A saturated aqueous sodium chloride solution was added and extracted with dichloromethane. The organic layer was dried over magnesium sulfate and concentrated in vacuo. Column chromatography was performed using hexane / ethyl acetate (80/20) as eluent [Rf = 0.41, hexane / ethyl acetate (80/20)] to give a white solid (yield 85%).

Spectral results

IR (KBr) (cm ^-1 ): 2295, 2922, 2632, 1635, 1482, 1455, 1424, 1380, 1276, 1247, 1129, 1086, 868, 839, 813

¹ H-NMR δ _H (CDCl ₃ , 250 MHz) 7.33 (s, 2H), 3.54 (q, 4H, J = 7.15 Hz), 3.12 (q, 4H, J = 7.15 Hz), 1.30-0.52 (m, 50H), 0.21 (s, 12H)

¹³ C-NMR δ _C (CDCl ₃ , 62.5 MHz) 172.4, 142.2, 137.3, 132.2, 43.3, 38.9, 33.7, 31.9, 29.7, 29.4, 24.0, 22.7, 16.0, 14.1, 13.8, 12.8, -2.3

Mass spectrometry: (CI) m / z = 644.5132

Elemental Analysis (C ₃₈ H ₇₂ N ₂ O ₂ Si, 645.17)

Measured value C: 70.84%, H: 11.26%, N: 4.39%

Calculated value C: 70.75%, H: 11.25%, N: 4.34%

Example 3

2-dimethyloctylsilyl-5-dimethyldecylsilyl-tetra- N Preparation of -ethyl-p-xylenediamine

Borane-tetrahydrofuran complex (23 ml, in a stirred solution in which 2-dimethyloctylsilyl-5-dimethyldecylsilyl-tetra- N -ethyl-terephthalamide (1.3 g, 2.3 mmol) was dissolved in 30 ml of anhydrous tetrahydrofuran. 23 mmol) was added. The reaction mixture was refluxed for 18 hours. Water was carefully added until hydrogen evolution ceased. The reaction mixture was concentrated in vacuo and 6M hydrochloric acid was added. The aqueous solution was heated to reflux for 4 hours. The reaction solution was cooled and pH was adjusted to 9 with sodium hydroxide. The aqueous layer was extracted with dichloromethane. The combined organic layers were dried over magnesium sulfate and concentrated in vacuo. Column chromatography was performed using hexane / ethyl acetate (96/4) as eluent [Rf = 0.79, hexane / ethyl acetate (80/20)] to give a white solid (yield 52%). mp = 26 ° C

Spectral results

IR (CHCl ₃ ) (cm ^-1 ): 2963, 2922, 2852, 1466, 1370, 1248, 1203, 1166, 1121, 1057, 835

¹ H-NMR δ _H (CDCl ₃ , 250 MHz) 7.71 (s, 2H), 3.63 (s, 4H), 2.51 (q, 8H, J = 7.10 Hz), 1.30-0.81 (m, 50H), 0.30 ( s, 12H)

¹³ C-NMR δ _C (CDCl ₃ , 62.5 MHz) 143.2, 137.821, 134.7, 58.6, 46.2, 33.7, 31.9, 29.7, 29.3, 24.2, 22.7, 16.6, 14.1, 11.7, -1.3

Mass spectrometry: (MALDI) m / z 618.30 ( MH ) ⁺

Example 4

Preparation of 2-dimethyldecylsilyl-5-dimethyldecylsilyl-1,4-bis (chloromethyl) benzene

Vinyl chloroformate (70.3 ml, 82.7) in 2-dimethyldecylsilyl-5-dimethyldecylsilyl-tetra- N -ethyl-p-xylenediamine (663 mg, 1.09 mmol) dissolved in 20 ml of anhydrous dichloromethane at 0 ° C. mmol) was added. The reaction mixture was stirred at rt for 5 h. A saturated aqueous sodium chloride solution was added, and the aqueous layer was extracted with dichloromethane. The combined organic layers were dried over magnesium sulfate and concentrated in vacuo. Column chromatography was performed using hexane as eluent (Rf = 0.46, hexane) to give a white solid (yield 65%). mp = 40 ° C

Spectral results

IR (CHCl ₃ ) (cm ^-1 ): 2923, 2854, 1466, 1411, 1377, 1344, 1254, 1192, 1172, 1140, 1108, 837, 792, 716

¹ H-NMR δ _H (CDCl ₃ , 250 MHz) 7.57 (s, 2H), 4.70 (s, 4H), 1.36-1.29 (m, 29H), 0.92-0.83 (m, 9H), 0.42 (s, 12H )

¹³ C-NMR δ _C (CDCl ₃ , 62.5 MHz) 141.9, 140.2, 137.0, 46.5, 33.6, 32.0, 29.7, 29.6, 29.4, 29.3, 24.0, 22.7, 16.5, 14.1, -1.5

Elemental analysis

Measured value C: 66.52%, H: 10.31%

Calculated value C: 66.38%, H: 10.41%

Example 5

Preparation of Poly [2- (dimethyloctylsilyl) -5- (dimethyldecylsilyl) -1,4-phenylene vinylene]

In degassing liquid in which 2-dimethyldecylsilyl-5-dimethyldecylsilyl-1,4-bis (chloromethyl) benzene (109 mg, 0.2 mmol) is dissolved in 1.5 ml of anhydrous tetrahydrofuran, A degassing liquid in which t-butoxy 롸 potassium (112.5 mg, 1 mmol) was dissolved in 5 ml of tetrahydrofuran was added over 10 minutes. The reaction mixture was stirred overnight under nitrogen gas. The reaction solution was then poured into methanol to give a pale yellow flake. The polymer was reprecipitated in acetone and dried overnight. (Yield 26%)

Spectral results

UV (CHCl ₃ ) δ _max : 438nm

UV (Film) δ _max : 430nm

Mn (GPC) 289000, Mw (GPC) 1065000, PD = 3.7

¹ H-NMR (CDCl ₃ , 250 MHz) d / ppm vs.

TGA: decomposes at 350 ° C

DSC: decomposition at 300 ° C., no Tg, no mp.

Example 6 Device Fabrication

Single and double layer devices were fabricated featuring a hole conduction / electron blocking layer of PEDOT: PSS on an ITO substrate equipped with two different cathode metals (Al, Ca). Single and double layer devices were fabricated. Quantitative data is only provided for bilayer devices with PEDOT: PSS layer.

Any one of THF, xylene or toluene was used as the spin coating solvent. In the case of DMOS-PPV, tetrachloroethane was used.

Table 1 below is data on the device fabricated with a 40 nm PEDOT: PSS hole conducting layer. All values represent maximum values.

PL Alcd / ㎡ Cacd / ㎡ Alcd / A Cacd / A ON Voltage 0.1 cd / ㎡ (0.01 cd / ㎡) For Al ON Voltage 0.1 cd / ㎡ (0.01 cd / ㎡) For Ca C ₈ C ₈ 3 HR50 47% 20 62 0.45 0.23 14 V (13 V) 13 V (12 V)  DMOS-PPV 6 FGB17671 57% 140 12 0.40 0.03 14 V 13 V (12 V) C ₈ C ₁₀ 8 FGC28139 57% 260 36 0.23 0.05 8 V (7 V) 6 V (5 V) C ₁₀ C ₁₀ 13 FGC28 138 53% 31 113 0.16 0.20 12 V (10 V) 7 V (6 V)

Film thickness 3: 100 nm; 6: 90 nm; 8: 70 nm; 13: 120 nm

Various spectral results are shown in FIGS. 1 to 5. The best results were obtained with Al cathodes in all other cases except C ₁₀ C ₁₀ polymer 13. The turn-on voltage with C ₈ C ₁₀ Polymer 8 was lower than with other materials (particularly with Al cathodes). The thickness of the light emitting layer can also be an important factor [C ₈ C ₁₀ Polymer 8 and C ₁₀ C ₁₀ Polymer 13 require the same field, which is necessary for C ₈ C ₈ Polymer 3 and DMOS-PPV 6 Lower than that).

The efficiency of DMOS-PPV devices contrasts well with previous studies using this polymer. The highest efficiency in this study was measured when using C ₈ C ₈ polymer 3, while the highest luminescence was achieved when using C ₈ C ₁₀ polymer 8. This finding holds that surprising advantages are maintained in preparing polymers having a first monomer comprising an asymmetric or heteroaromatic group according to the present invention.

Claims (45)

(i) preparing an aromatic group or heteroaromatic group substituted with the first and second director groups, (ii) performing metallization at the first position of the aromatic group or heteroaromatic group, and (iii) electrophilicity (A) preparing a first monomer including a substituted or heteroaromatic group by introducing a first substituent into the first position by performing a substitution reaction; Contacting said first monomer with at least two additional monomers, each of which is the same as or different from said first monomer, under conditions capable of producing a polymer or oligomer in the reaction mixture, Wherein the properties and positions of the first and second director groups are position-selected to the first position. The process according to claim 1, wherein the step (a) (iv) performing metallization at the second position of the aromatic group or heteroaromatic group, and (v) conducting an electrophilic substitution reaction to introduce a second substituent at the second position , Wherein the characteristics and position of the first and second director groups are position select the second position. The compound of claim 1, wherein the first and / or second substituents are each halide, B (OH) ₂ , B (OR) ₂ , organotin, alkoxy, alkoxyalkyl, alkyl, hydroxide, Aryl, heteroaryl, silyl, triflate and amide and COCF ₃ . The method of claim 3, wherein the first and / or second substituents are each selected from the group consisting of Br, I, SiMe ₂ C ₈ H ₁₇ , SiMe ₂ C ₁₀ H _21, and SiMe ₃ . The process according to claim 1 or 2, wherein the metallization is carried out by the addition of organolithium. 3. A method according to claim 1 or 2, wherein the properties and positions of the first and second director groups are selected so that the first position is ortho to the first director group. 3. The method of claim 2, wherein the properties and positions of the first and second director groups are selected so that the second position is ortho to the second director group. 4. The method of claim 1 or 2, wherein the first and second director groups are the same as or different from each other, and each of an alkoxy group, an alkoxyalkyl group, an amide group, a halide group, a haloalkyl group, an amino group, an aminoalkyl group, a carboxylic acid ester group, The urethane group, carbamate group, sulfonamide group, sulfuryl alkyl group or carbamide group. The method of claim 8, wherein the first and second director groups are the same as or different from each other, and each of CONEt ₂ , CONHCMe ₂ Ph, OCONMeCMe ₂ Ph, OCONEt ₂ , SO ₂ NHCMe ₂ Ph, and SO ₂ -tBu, respectively. The production method selected. The manufacturing method according to claim 1 or 2, wherein the first director group and the second director group are different from each other. The manufacturing method according to claim 1 or 2, wherein the first director group and the second director group are identical to each other. The process according to claim 1 or 2, wherein the aromatic group or heteroaromatic group is selected from phenylene, fluorene, anthracene or naphthalene groups. The process according to claim 1, wherein the step (a) has two reactive groups participating in the polymerization by converting one or both of the director groups and / or one or both of the first and second substituents to a reactive group, respectively. The production method further comprises the step (vi) of producing a monomer. The method of claim 13, wherein the two reactive groups are in para position with one another. The production method according to claim 13 or 14, wherein each director group is independently converted to a phosphonate group, carbonyl group, triflate group, or halomethyl group. The method of claim 15, wherein the polymer or oligomer comprises arylene vinylene repeat units derived from a first monomer. The method of claim 16, wherein the arylene vinylene repeating unit comprises a phenylene vinylene group. The production method according to claim 13 or 14, wherein each substituent is independently converted to a halide group. The method of claim 18, wherein the polymer or oligomer comprises phenylene repeat units derived from a first monomer. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete